There has recently been an increased interest in electrochemistry and electrochemical phenomena of polymeric systems. See, in this regard, U.S. Pat. Nos. 4,222,903 and 4,204,216--Heeger et al. and 4,321,114 and 4,442,187--MacDiarmid et al. which are directed to the electrochemistry of certain conjugated polymers having extended conjugation in at least one backbone chain thereof. Each of the foregoing are incorporated herein by reference.
While interest has also been directed at certain non-conjugated polymers, including certain forms of the polyanilines, work in that area has not met with successful development of secondary batteries, fuel cells, or substantially reversible electrochemical methods. Jozefowicz et al., has undertaken certain electrochemical studies of certain forms of polyaniline as an anode and cathode in aqueous solution. See, for example French Patent 1,519,729; French Patent of Addition No. 94,536; U.K. Patent 1,216,549; "Direct Current Conductivity of Polyaniline Sulfates", M. Doriomedoff, F. Hautiere-Cristofini, R. DeSurville, M. Jozefowicz, L-T. Yu, and R. Buvet, J. Chim. Phys, Physicochim. Biol. 68, 1055 (1971); "Continuous Current Conductivity of Macromolecular Materials", L-T. Yu, M. Jozefowicz, and R. Buvet, Chim. Macromol. 1, 469 (1970); "Polyaniline-Based Filmogenic Organic-Conductor Polymers", D. LaBarre and M. Jozefowicz, C. R. Acad. Sci., Ser. C, 269, 964 (1969); "Recently Discovered Properties of Semiconducting Polymers", M. Jozefowicz, L-T. Yu, J. Perichon, and R. Buvet, J. Polym. Sci., Part C, 22, 1187 (1967); "Electrochemical Properties of Polyaniline Sulfates", F. Cristofini, R. DeSurville, and M. Jozefowicz, C. R. Acad. Sci., Ser. C, 268, 1346 (1969 ); "Electrochemical Cells Using Protolytic Organic Semiconductors", R. DeSurville, M. Jozefowicz, L-T. Yu, J. Perichon, and R. Buvet, Electrochim. Acta, 13, 1451 (1968); "Oligomers and Polymers Produced by Oxidation of Aromatic Amines", R. DeSurville, M. Jozefowicz, and R. Buvet, Ann. Chim. (Paris), 2, 5 (1967); "Experimental Study of the Direct Current Conductivity of Macromolecular Compounds", L-T. Yu, M. Borredon, M. Jozefowicz, G. Belorgey, and R. Buvet, J. Polym. Sci., Polym. Symp., 16, 2931 (1967); "Conductivity and Chemical Properties of Oligomeric Polyanilines", M. Jozefowicz, L-T. Yu, G. Belorgey, and R. Buvet, J. Polym. Sci., Polym. Symp., 16, 2934 (1967); "Products of the Catalytic Oxidation of Aromatic Amines", R. DeSurville, M. Jozefowicz, and R. Buvet, Ann. Chim. (Paris), 2, 149 (1967); "Conductivity and Chemical Composition of Macromolecular Semiconductors", L-T. Yu and M. Jozefowicz, Rev. Gen. Electr., 75, 1014 (1966); "Relation Between the Chemical and Electrochemical Properties of Macromolecular Semiconductors", M. Jozefowicz and L-T. Yu, Rev. Gen. Electr., 75, 1008 (1966); "Preparation, Chemical Properties, and Electrical Conductivity of Poly-N-Alkylanilines in the Solid State", D. Muller and M. Jozefowicz, Bull. Soc. Chim. Fr., 4087 (1972). Jozefowicz et al. employed a reduced form and an oxidized form of polyaniline, neither of which was analyzed or characterized in any way as to their chemical composition, as the anode and cathode respectively in one normal sulphuric acid (pH=0). They observed that such an electrochemical cell could be charged and discharged for two consecutive cycles.
Repetition of the disclosures of Jozefowicz by the inventors of this invention (see the Examples hereto) has shown that the methods of Jozefowicz do not lead to substantial reversibility of electrochemistry involving polyaniline or to electrochemical cells having sufficient reversibility as to provide practical utility for secondary battery use.
An attempt at the preparation of secondary batteries from polyaniline was reported by Kitani et al. at the 24th Annual Battery Conference in Osaka, Japan on Nov. 9-14, 1983, entitled "Secondary Batteries Using Polyaniline". These anhydrous systems are dissimilar from the instant invention.